Chlorinated vinyl chloride resin

ABSTRACT

The present invention provides a chlorinated polyvinyl chloride resin that enables the production of a molded article that maintains high adhesion strength even when used in a form subjected to high pressure and is less susceptible to defects such as cracks due to insufficient strength, as well as a resin composition for molding and a molded article each including the chlorinated polyvinyl chloride resin. Provided is a chlorinated polyvinyl chloride resin, containing two components including a A30 component and a B30 component, the A30 component and the B30 component being determined by measuring the resin by a solid echo method using pulse NMR at 30° C. to give a free induction decay curve of 1H spin-spin relaxation, and subjecting the free induction decay curve to waveform separation into two curves derived from the A30 component and the B30 component in order of shorter relaxation time using the least square method, and having a ratio of T5B to TB [T5B/TB] of 76% or more and less than 96%, where TB is a relaxation time of the B30 component and T5B is a relaxation time of the B30 component after heating at 200° C. for five minutes.

TECHNICAL FIELD

The present invention relates to a chlorinated polyvinyl chloride resinthat enables the production of a molded article that maintains highadhesion strength even when used in a form subjected to high pressureand is less susceptible to defects such as cracks due to insufficientstrength, as well as a resin composition for molding and a moldedarticle each including the chlorinated polyvinyl chloride resin.

BACKGROUND ART

Polyvinyl chloride resins generally have excellent mechanical strength,weather resistance, and chemical resistance, and thus have beenprocessed into various molded articles and used in various fields.

Polyvinyl chloride resins, however, have poor heat resistance. This hasled to the development of chlorinated polyvinyl chloride resins (CPVCs),which are polyvinyl chloride resins chlorinated to have improved heatresistance.

For example, Patent Literature 1 discloses a composition containingpost-chlorinated polyvinyl chloride in combination with a specificstabilizer. Patent Literature 1 discloses that such a resin canwithstand thermal stress and mechanical stress during processing.

CITATION LIST Patent Literature

-   Patent Literature 1: JP H8-311286 A

SUMMARY OF INVENTION Technical Problem

However, a molded article (e.g., a pipe or a joint) obtained using thechlorinated polyvinyl chloride resin disclosed in Patent Literature 1may not have sufficient adhesion strength especially when used in a formsubjected to high pressure, and may be disconnected or cause waterleakage.

Moreover, the obtained molded article may have low fusion strength at aspider portion when used as a pipe, or may have low fusion strength at aweld portion when used as a joint. Such a molded article thus may crackwhen used as a joint or the like.

In view of the above issues in the prior art, the present invention aimsto provide a chlorinated polyvinyl chloride resin that enables theproduction of a molded article that maintains high adhesion strengtheven when used in a form subjected to high pressure and is lesssusceptible to defects such as cracks due to insufficient strength, aswell as a resin composition for molding and a molded article eachincluding the chlorinated polyvinyl chloride resin.

Solution to Problem

The present invention provides a chlorinated polyvinyl chloride resin,containing two components including a A₃₀ component and a B₃₀ component,the A₃₀ component and the B₃₀ component being determined by measuringthe resin by a solid echo method using pulse NMR at 30° C. to give afree induction decay curve of ¹H spin-spin relaxation, and subjectingthe free induction decay curve to waveform separation into two curvesderived from the A₃₀ component and the B₃₀ component in order of shorterrelaxation time using the least square method, and having a ratio ofT5_(B) to T_(B) [T5_(B)/T_(B)] of 76% or more and less than 96%, whereT_(B) is a relaxation time of the B₃₀ component and T5_(B) is arelaxation time of the B₃₀ component after heating at 200° C. for fiveminutes.

The present invention is described in detail below.

The chlorinated polyvinyl chloride resin that is an embodiment of thepresent invention has a ratio of T5_(B) to T_(B) [T5_(B)/T_(B)] of 76%or more and less than 96%, where T_(B) is a relaxation time of the B₃₀component obtained by measuring the resin by a solid echo method usingpulse NMR at 30° C. and T5_(B) is a relaxation time of the B₃₀ componentafter heating at 200° C. for five minutes.

When the ratio [T5_(B)/T_(B)] of the relaxation time T5_(B) of the B₃₀component after heating at 200° C. for five minutes to the relaxationtime T_(B) is 76% or more and less than 96%, it is possible to produce amolded article that maintains high adhesion strength even when used in aform subjected to high pressure and that is less susceptible to defectssuch as cracks due to insufficient strength. The T5_(B)/T_(B) ispreferably 78% or more and 95% or less. The T5_(B)/T_(B) is morepreferably 80% or more and 94% or less, still more preferably 81% ormore and 92% or less.

The ratio of the relaxation time T5_(B) of the B₃₀ component afterheating at 200° C. for five minutes to the relaxation time T_(B) of theB₃₀ component refers to T5_(B)/T_(B)expressed in percentage.

Herein, pulse NMR refers to an analysis involving detecting a responsesignal to a pulse to obtain a ¹H nuclear magnetic relaxation time of asample. A free induction decay curve may be obtained as a pulseresponse.

The free induction decay curve consists of overlapped multiple freeinduction decay curves derived from multiple components having differentrelaxation times. The relaxation times or the components thereof of thecomponents having different relaxation times can be identified bywaveform separation of the curve using the least square method. Analysisinvolving separation into three components using pulse NMR describedabove is a known technique. Examples of literatures describing thetechnique include JP 2018-2983 A.

The pulse NMR identifies two components, a A₃₀ component and a B₃₀component. The A₃₀ component is a component having a short relaxationtime in pulse NMR measurement and refers to a hard component with lowmolecular mobility. The B₃₀ component is a component having a longrelaxation time in pulse NMR measurement and refers to a soft componentwith high molecular mobility.

The relaxation time T_(B) of the B₃₀ component is preferably 0.140 ms orlonger and 0.180 ms or shorter. When the relaxation time T_(B) is withinthe above range, the surface of the molded article can have bettersolvent-swellability when a polyvinyl chloride adhesive is used, thusimproving adhesion strength. Moreover, melting under heat startsearlier, which can improve fusion strength in a mold that has a portionwhere flows of molten resin join together during molding.

The lower limit of the relaxation time T_(B) is more preferably 0.150ms, and the upper limit thereof is more preferably 0.170 ms.

The relaxation time T_(B) means a relaxation time measured withoutheating the chlorinated polyvinyl chloride resin.

In the present invention, the relaxation time T5_(B) of the B₃₀component after heating at 200° C. for five minutes is preferably 0.110ms or longer and 0.150 ms or shorter. When the relaxation time T5_(B) iswithin the above range, the surface of the molded article can havebetter solvent-swellability when a polyvinyl chloride adhesive is used,thus improving adhesion strength. Moreover, melting under heat startsearlier, which can improve fusion strength in a mold that has a portionwhere flows of molten resin join together during molding.

The lower limit of the relaxation time T5_(B) is more preferably 0.115ms, and the upper limit thereof is more preferably 0.145 ms.

The relaxation time T5_(B) means a relaxation time after heating thechlorinated polyvinyl chloride resin at 200° C. for five minutes.

In the present invention, a ratio of T5_(B) to T20_(B) [T5_(B)/T20_(B)]is preferably 76% or more and less than 96%, where T5_(B) is therelaxation time of the B₃₀ component after heating at 200° C. for 5minutes and T20_(B) is a relaxation time of the B₃₀ component afterheating at 200° C. for 20 minutes. When the ratio is within the aboverange, the surface of the molded article can have bettersolvent-swellability when a polyvinyl chloride adhesive is used, thusimproving adhesion strength. Moreover, melting under heat startsearlier, which can improve fusion strength in a mold that has a portionwhere flows of molten resin join together during molding. The ratio ismore preferably 78% or more and 95% or less, still more preferably 80%or more and 94% or less, particularly preferably 81% or more and 92% orless.

In the present invention, the relaxation time T20_(B) of the B₃₀component after heating at 200° C. for 20 minutes is preferably 0.110 msor longer and 0.150 ms or shorter. When the relaxation time T20_(B) iswithin the above range, the surface of the molded article can havebetter solvent-swellability when a polyvinyl chloride adhesive is used,thus improving adhesion strength. Moreover, melting under heat startsearlier, which can improve fusion strength in a mold that has a portionwhere flows of molten resin join together during molding. The lowerlimit of the relaxation time T20_(B) is more preferably 0.115 ms, andthe upper limit thereof is more preferably 0.145 ms.

The relaxation time T20_(B) means a relaxation time after heating thechlorinated polyvinyl chloride resin at 200° C. for 20 minutes.

In the present invention, a relaxation time T_(A) of the A₃₀ componentis preferably 0.010 ms or longer and shorter than 0.012 ms.

The relaxation time T_(A) means a relaxation time measured withoutheating the chlorinated polyvinyl chloride resin.

The chlorinated polyvinyl chloride resin that is an embodiment of thepresent invention preferably has a percentage of the A₃₀ component [A₃₀component/(A₃₀ component+B₃₀ component)] of 90% or more and less than100%.

The chlorinated polyvinyl chloride resin that is an embodiment of thepresent invention preferably has a percentage of the B₃₀ component [B₃₀component/(A₃₀ component+B₃₀ component)] of 1% or more and 10% or less.

The chlorinated polyvinyl chloride resin that is an embodiment of thepresent invention preferably contains structural units (a) to (c)represented by the following formulas (a) to (c). Preferably, theproportion of the structural unit (a) is 5.0 mol % or higher, theproportion of the structural unit (b) is 40.0 mol % or lower, and theproportion of the structural unit (c) is 55.0 mol % or lower, relativeto the total number of moles of the structural units (a), (b), and (c).This allows the surface of the molded article to have bettersolvent-swellability when a polyvinyl chloride adhesive is used, thusimproving adhesion strength. This also allows melting under heat tostart earlier, which can improve fusion strength in a mold that has aportion where flows of molten resin join together during molding.

In the chlorinated polyvinyl chloride resin that is an embodiment of thepresent invention, the proportion of the structural unit (a) is morepreferably 30.0 mol % or higher, still more preferably 35.0 mol % orhigher, and preferably 90.0 mol % or lower, more preferably 60.0 mol %or lower, relative to the total number of moles of the structural units(a), (b), and (c).

The proportion of the structural unit (b) is preferably 5.0 mol % orhigher, more preferably 15.0 mol % or higher, and more preferably 30.0mol % or lower, still more preferably 25.0 mol % or lower, relative tothe total number of moles of the structural units (a), (b), and (c).

The proportion of the structural unit (c) is preferably 5.0 mol % orhigher, more preferably 25.0 mol % or higher, and more preferably 55.0mol % or lower, still more preferably 40.0 mol % or lower, relative tothe total number of moles of the structural units (a), (b), and (c).

[Chem. 1]

—CH₂—CHCl—  (a)

—CH₂—CCl₂—  (b)

—CHCl—CHCl—  (c)

The molar ratios of the structural units (a), (b), and (c) in thechlorinated polyvinyl chloride resin that is an embodiment of thepresent invention reflect the site to which chlorine is introduced atthe time of chlorination of the polyvinyl chloride resin (PVC). The PVCprior to chlorination is in a state where it is mostly constituted bythe structural unit (a) and the proportions of the structural units (b)and (C) are 0 mol %. As chlorination proceeds, the proportion of thestructural unit (a) decreases, while the proportions of the structuralunits (b) and (c) increase. At this time, nonuniformity of thechlorinated state will increase in a case where the proportion of thestructural unit (b), which is unstable, excessively increases, or in acase where the chlorinated site and the unchlorinated site are unevenlypresent within the same particle of the chlorinated polyvinyl chlorideresin. The surface of the molded article can have bettersolvent-swellability when a polyvinyl chloride adhesive is used, thusimproving adhesion strength. Moreover, melting under heat can startearlier, which can improve fusion strength in a mold that has a portionwhere flows of molten resin join together during molding.

The molar ratios of the structural units (a), (b), and (c) in thechlorinated polyvinyl chloride resin that is an embodiment of thepresent invention can be measured by molecular structure analysis usingNMR. NMR analysis can be performed in accordance with the methoddescribed in R. A. Komoroski, R. G. Parker, J. P. Shocker,Macromolecules, 1985, 18, 1257-1265.

The chlorinated polyvinyl chloride resin that is an embodiment of thepresent invention may contain a different structural unit other than thestructural units (a), (b), and (c) as long as the effects of the presentinvention are not impaired.

The amount of the different structural unit is preferably 0% by mass ormore, and preferably less than 10% by mass.

Examples of the different structural unit include a structural unithaving a sulfur-containing substituent and the like.

Examples of the sulfur-containing substituent include substituentsderived from sulfur compounds and the like.

In the chlorinated polyvinyl chloride resin, a sulfur content (describedlater) of the chlorinated polyvinyl chloride resin of higher than 0 massppm indicates that sulfur is present in the resin and that the sulfur isbound to the resin. This shows that the chlorinated polyvinyl chlorideresin contains a structural unit having a sulfur-containing substituent.

Examples of the sulfur-containing substituent include substituentsderived from sulfur compounds. Examples of the sulfur compounds includecompounds described later. Preferred among these is at least onethioglycolic acid compound selected from the group consisting ofthioglycolic acid and a thioglycolic acid ester.

Examples of the structural unit having a sulfur-containing substituentinclude a structural unit (d) represented by the following formula (d).R in the structural unit (d) is preferably a group to which is bound atleast one selected from the group consisting of an alkylene group, anester group, an alkyl group, and a thiol group, more preferably a groupto which is bound at least one selected from the group consisting of analkylene group, an ester group, and an alkyl group.

The chlorinated polyvinyl chloride resin that is an embodiment of thepresent invention preferably has a sulfur content of 5 mass ppm or moreand 1,000 mass ppm or less. The sulfur content is more preferably 10mass ppm or more and 500 mass ppm or less. The sulfur content is stillmore preferably 200 mass ppm or less.

The sulfur content of the chlorinated polyvinyl chloride resin can bedetermined by quantitative analysis using ion chromatography (IC).Specifically, the chlorinated polyvinyl chloride resin is dissolved inTHF and put in a centrifuge to separate/filter out insoluble componentsfrom the solution. An excessive amount of methanol is then added forreprecipitation, and the precipitate is separated by suction filtrationand dried in a vacuum drier at 80° C. The resulting sample is weighed ina ceramic boat and then burned in an automatic sample combustion device.The generated gas is captured in 10 mL of an absorber liquid. Thisabsorber liquid is adjusted to 15 mL with ultrapure water, and subjectedto IC quantitative analysis. For example, an automatic combustion device(produced by Mitsubishi Chemical Analytech, AQF-2100H) and an IC(produced by Thermo Fisher Scientific, ICS-5000) are used formeasurement. Thus, the sulfur content (mass ppm) of the chlorinatedpolyvinyl chloride resin can be quantified.

In the chlorinated polyvinyl chloride resin that is an embodiment of thepresent invention, the amount of added chlorine is preferably 1.0% bymass or more and is preferably 16.0% by mass or less.

When the amount of added chlorine is 1.0% by mass or more, a moldedarticle to be obtained has sufficient heat resistance. When the amountof added chlorine is 16.0% by mass or less, moldability is improved.

The amount of added chlorine is more preferably 3.2% by mass or more,still more preferably 6.2% by mass or more. The amount is morepreferably 15.2% by mass or less, still more preferably 12.2% by mass orless.

A polyvinyl chloride resin typically has a chlorine content of 56.8% bymass. The amount of added chlorine means the proportion of chlorineintroduced into a polyvinyl chloride resin, and can be measured by themethod specified in JIS K 7229.

The degree of polymerization of the chlorinated polyvinyl chloride resinthat is an embodiment of the present invention is preferably 100 orhigher, more preferably 400 or higher, still more preferably 500 orhigher. The degree of polymerization is preferably 2,000 or lower, morepreferably 1,500 or lower.

When the degree of polymerization is within the above range, fluidity inmolding and the strength of the molded article can both be achieved.

The chlorinated polyvinyl chloride resin that is an embodiment of thepresent invention may be produced by, for example, a method includingpreparing a suspension in a reaction vessel by suspending a polyvinylchloride resin in an aqueous medium, introducing chlorine into thereaction vessel, and heating the suspension to chlorinate the polyvinylchloride resin (chlorination step).

In particular, the chlorinated polyvinyl chloride resin having a ratio[T5_(B)/T_(B)] of the relaxation time T5_(B) of the B₃₀ component afterheating at 200° C. for five minutes to the relaxation time T_(B) of theB₃₀ component within a predetermined range can be produced by adjustingthe average degree of polymerization and addition concentration of thepolyvinyl chloride used, the average chlorine consumption rate, thereaction method (photo-chlorination or thermal chlorination), thereaction temperature, and the reaction pressure in the chlorinationstep, adding a sulfur compound after the chlorination step, andadjusting the amount of the sulfur compound added.

The reaction vessel used may be a commonly used vessel such as aglass-lined stainless steel reaction vessel or titanium reaction vessel,for example.

The method of preparing the suspension of the polyvinyl chloride resinin an aqueous medium is not limited. For example, a cake-like PVCobtained by subjecting a polymerized PVC to monomer removal treatmentmay be used, or a dried PVC may be resuspended in an aqueous medium, ora suspension obtained by removing any substance undesired for thechlorination reaction from the polymerization system may be used. It ispreferred to use a cake-like resin obtained by subjecting a polymerizedPVC to monomer removal treatment.

The aqueous medium used may be ion-exchange-treated pure water, forexample. While the amount of the aqueous medium is not limited,generally, it is preferably 150 to 400 parts by mass based on 100 partsby mass of the PVC.

In the chlorination step, the concentration of the polyvinyl chlorideresin in the aqueous medium suspension (addition concentration) ispreferably 20 to 40% by mass.

Chlorine to be introduced into the reaction vessel may be either liquidchlorine or gaseous chlorine. The use of liquid chlorine is efficient inthat a large amount of chlorine can be charged into the reaction vesselin a short period of time. Chlorine may be added in the course ofreaction to adjust the pressure or supply chlorine. At this time,gaseous chlorine in addition to liquid chlorine may be blown into thereaction vessel, as required. It is preferred to use chlorine afterpurging 5 to 10% by mass of chlorine from the cylinder.

While the reaction pressure (gauge pressure in the reaction vessel) inthe chlorination step is not limited, it is preferably from 0 to 2 MPa,more preferably from 0.01 to 0.3 MPa because the higher the chlorinepressure is, the more readily the chlorine will penetrate into the PVCparticles.

The method of chlorinating the PVC in the suspended state is notlimited. Examples of the chlorination method include a method in whichlight energy such as ultraviolet light is applied to acceleratechlorination by photoreaction (hereinafter referred to asphoto-chlorination). The use of light energy such as ultraviolet lightrequires an apparatus capable of light energy irradiation such asultraviolet irradiation under high temperature and high pressureconditions.

The reaction temperature in the chlorination step is preferably 30° C.to 130° C. In particular, the reaction temperature in the chlorinationstep performed by photo-chlorination is preferably 30° C. to 90° C.,more preferably 40° C. to 80° C. In the photo-chlorination, the ratio ofthe light energy irradiation intensity (W) to the total amount (kg) ofthe raw material PVC and water is preferably 0.001 to 6 (W/kg). Theirradiation light preferably has a wavelength of 280 to 420 nm.

The photo-chlorination can provide a chlorinated polyvinyl chlorideresin that enables the production of a molded article that has excellentgloss as well as high heat resistance and high mechanical strength.

In the chlorination, preferably, hydrogen peroxide is further added tothe suspension. Adding hydrogen peroxide can improve the speed ofchlorination. The hydrogen peroxide is added preferably in an amount of5 to 500 ppm relative to the PVC per hour of reaction time. Adding toolittle hydrogen peroxide does not provide the effect of improving thespeed of chlorination. Adding too much hydrogen peroxide decreases thethermal stability of the CPVC.

When the hydrogen peroxide is added, the heating temperature can berelatively low because the hydrogen peroxide improves the speed ofchlorination. The heating temperature may be within the range of 65° C.to 110° C., for example.

In the chlorination step, the average chlorine consumption rate ispreferably within the range of 0.01 to 0.025 kg/PVC-Kg-5 min. As usedherein, the term “average chlorine consumption rate” refers to theamount of chlorine consumed in 5 minutes per kilogram of the rawmaterial PVC.

When chlorination is performed using the above method, a CPVC havingless nonuniformity in the chlorinated state and having excellent thermalstability can be obtained.

In the chlorination method, the concentration of the chlorine introducedinto the reaction vessel is preferably 99.5% or higher.

For production of the chlorinated polyvinyl chloride resin, a sulfurcompound is preferably added after the chlorination step.

The chlorination step is typically followed by a neutralizing step, awashing step, a dehydrating step, and a drying step in sequence. Thestep of adding a sulfur compound is preferably performed during or afterthe dehydrating step. The sulfur compound may be added all at once or inmultiple portions. The sulfur compound may be added as is, or may bediluted in a solvent such as water before being added.

Adding a sulfur compound causes addition reaction of the sulfur compoundto replace the chlorine that is released from the main chain of thechlorinated polyvinyl chloride resin in the subsequent drying step. As aresult, the dehydrochlorination amount during molding is reduced, andthus thermal stability is improved.

The sulfur compound is preferably an organic sulfur compound. Specificexamples thereof include thioglycolic acid compounds, thiourea,thioglycerin, thioacetic acid, potassium thioacetate, thiodiacetic acid,thiosemicarbazide, and thioacetamide.

In particular, the sulfur compound is more preferably at least onethioglycolic acid compound selected from the group consisting ofthioglycolic acid and a thioglycolic acid ester.

The thioglycolic acid encompasses not only thioglycolic acid but alsothioglycolic acid salts such as metal salts, ammonium salts, and aminesalts of thioglycolic acid.

Examples of the thioglycolic acid salts include sodium thioglycolate,calcium thioglycolate, ammonium thioglycolate, methylaminethioglycolate, ethylamine thioglycolate, monoethanolamine thioglycolate,diethanolamine thioglycolate, and triethanolamine thioglycolate.

Examples of the thioglycolic acid ester include thioglycolic acid alkylesters such as methyl thioglycolate, ethyl thioglycolate, n-butylthioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octylthioglycolate, isooctyl thioglycolate, decyl thioglycolate, and dodecylthioglycolate. Also usable is an ester of thioglycolic acid with ahydrocarbon containing an alkoxy group, such as methoxybutylthioglycolate.

Examples of the thioglycolic acid ester further include an alkanedioldithioglycolate which is a thioglycolic acid ester of an alkanediol, analkanepolyol polythioglycolate which is a thioglycolic acid ester of analkanepolyol, and polyalkylene glycol dithioglycolate which is athioglycolic acid ester of polyalkylene glycol.

Examples of the alkanediol dithioglycolate include ethylene glycolbisthioglycolate, butanediol bisthioglycolate, neopentylglycolbisthioglycolate, and hexanediol bisthioglycolate.

Examples of the alkanepolyol polythioglycolate includetrimethylolpropane tris(thioglycolate), pentaerythritoltris(thioglycolate), pentaerythritol tetrakis(thioglycolate), anddipentaerythritol hexa(thioglycolate).

Examples of the polyalkylene glycol dithioglycolate include diethyleneglycol dithioglycolate.

The thioglycolic acid compound is preferably a compound represented byHSCH₂COOR (wherein R is H or an alkyl group). The alkyl group has acarbon number of preferably 1 to 8.

In the production method, the lower limit of the amount of the sulfurcompound added relative to 100 parts by mass of the chlorinatedpolyvinyl chloride resin is preferably 0.001 parts by mass, and theupper limit thereof is preferably 10 parts by mass. Adding the sulfurcompound in an amount within the above range makes it possible to obtainthe chlorinated polyvinyl chloride resin. The upper limit is morepreferably 1 part by mass, still more preferably 0.5 parts by mass.

The sulfur compound may be added by any method, and is preferably addedat an addition rate of 20 to 500 g/min.

The drying temperature after adding the sulfur compound is preferably60° C. to 120° C.

The drying time is preferably 6 to 48 hours. The drying temperature andthe drying time within the above ranges promote the addition reaction ofthe sulfur compound. Examples of the drying method include stationarydrying, hot-air drying, fan drying, far infrared heat drying, and vacuumdrying.

A molded article can be produced by molding a resin composition formolding containing the chlorinated polyvinyl chloride resin.

The present invention also encompasses a resin composition for moldingcontaining the chlorinated polyvinyl chloride resin.

The lower limit of the amount of the chlorinated polyvinyl chlorideresin in the resin composition for molding is preferably 65% by mass,more preferably 70% by mass, and the upper limit thereof is preferably96% by mass, more preferably 93% by mass.

The resin composition for molding that is an embodiment of the presentinvention may optionally contain additives such as stabilizers,lubricants, processing aids, impact resistance modifiers, heatresistance improvers, antioxidants, ultraviolet absorbents, lightstabilizers, fillers, thermoplastic elastomers, pigments, andreinforcement materials.

Examples of the stabilizers include, but are not limited to, thermalstabilizers and thermal stabilization aids. Examples of the thermalstabilizers include, but are not limited to, organotin stabilizers, leadstabilizers, calcium-zinc stabilizers, barium-zinc stabilizers, andbarium-cadmium stabilizers.

Examples of the organotin stabilizers include dibutyl tin mercapto,dioctyl tin mercapto, dimethyl tin mercapto, dibutyl tin mercapto,dibutyl tin maleate, dibutyl tin maleate polymers, dioctyl tin maleate,dioctyl tin maleate polymers, dibutyl tin laurate, and dibutyl tinlaurate polymers.

Examples of the lead stabilizers include lead stearate, dibasic leadphosphite, and tribasic lead sulfate. These may be used singly or incombination of two or more thereof.

Examples of the thermal stabilization aids include, but are not limitedto, epoxidized soybean oil, phosphate, polyol, hydrotalcite, andzeolite. These may be used singly or in combination of two or morethereof.

Examples of the lubricants include internal lubricants and externallubricants.

The internal lubricants are used to reduce the fluid viscosity of themolten resin in molding to prevent the generation of frictional heat.Examples of the internal lubricants include, but are not limited to,butyl stearate, lauryl alcohol, stearyl alcohol, epoxidized soybean oil,glycerol monostearate, stearic acid, and bisamide. These may be usedsingly or in combinations of two or more.

The external lubricants are used to improve the slip effect betweenmetal surfaces and the molten resin in molding. Examples of the externallubricants include, but are not limited to, paraffin wax, polyolefinwaxes, ester waxes, and montanic acid wax. These may be used singly orin combinations of two or more.

Examples of the processing aids include, but are not limited to, acrylicprocessing aids such as alkyl acrylate-alkyl methacrylate copolymershaving a mass average molecular weight of 100,000 to 2,000,000. Examplesof the acrylic processing aids include, but are not limited to, n-butylacrylate-methyl methacrylate copolymers and 2-ethylhexyl acrylate-methylmethacrylate-butyl methacrylate copolymers. These may be used singly orin combination of two or more thereof.

Examples of the impact resistance modifiers include, but are not limitedto, methyl methacrylate-butadiene-styrene copolymers (MBS), chlorinatedpolyethylene, and acrylic rubber.

Examples of the heat resistance improvers include, but are not limitedto, α-methylstyrene resins and N-phenylmaleimide resins.

The lower limit of the amount of the impact resistance modifier in theresin composition for molding is preferably 1% by mass, more preferably2% by mass, and the upper limit thereof is preferably 30% by mass, morepreferably 15% by mass.

The impact resistance modifier in an amount in the above range cansufficiently increase the strength of the resulting molded article.

Examples of the antioxidants include, but are not limited to, phenolicantioxidants.

Examples of the light stabilizers include, but are not limited to,hindered amine light stabilizers.

Examples of the ultraviolet absorbents include, but are not limited to,salicylate ultraviolet absorbents, benzophenone ultraviolet absorbents,benzotriazole ultraviolet absorbents, and cyanoacrylate ultravioletabsorbents.

Examples of the fillers include, but are not limited to, calciumcarbonate and talc.

Examples of the pigments include, but are not limited to, organicpigments such as azo pigments, phthalocyanine pigments, threne pigments,and dye lake pigments; and inorganic pigments such as oxide pigments,molybdenum chromate pigments, sulfide/selenide pigments, andferrocyanide pigments.

Examples of the reinforcement materials include, but are not limited to,fiber reinforcement materials and non-fiber reinforcement materials.Examples of fiber reinforcement materials include glass fibers, carbonfibers, aramid fibers, polyethylene terephthalate fibers, cellulosenanofibers (CNF), and kenaf. Examples of non-fiber reinforcementmaterials include graphite and graphene.

Moreover, a molded article molded from the resin composition for moldingthat is an embodiment of the present invention is provided. The presentinvention also encompasses such a molded article.

Here, for the molded article, the chlorinated polyvinyl chloride resinin the molded article can be extracted with an organic solvent or thelike to measure the ratio [T5_(B)/T_(B)] of the relaxation time T5_(B)of the B₃₀ component after heating at 200° C. for five minutes to therelaxation time T_(B) of the B₃₀ component of the chlorinated polyvinylchloride resin.

The molded article may contain a reinforcement material such as glassfiber or carbon fiber.

The molding method may be any conventionally known molding method, forexample, extrusion molding or injection molding.

The molded article that is an embodiment of the present invention hasexcellent thermal stability and good appearance. The molded article cantherefore be suitably used in applications such as building components,plumbing materials and equipment, and housing materials.

It is known that, if conventional members of transportation machinery orbattery systems are faultily manufactured or inappropriately used, thebattery cells may ignite. As the capacity of battery cells has beenincreased to meet the demand for more convenience such as extension ofcruise mileage, the risk of ignition is increasing. Nowadays, batterysystems for transportation machinery are often mounted at places nearcrew members, such as vehicle compartments. With conventional safetymeasures, it is difficult to ensure sufficient evacuation time (aboutfive minutes) for crew members in the event of ignition. Thus, newsafety measures are awaited.

Conventional battery pack covers are made from iron. To meet the demandfor reducing the weight, replacing iron with aluminum or resin issuggested. However, if battery cells in battery systems ignite, aluminumor resin covers cannot prevent flame and smoke from occurring. Measuresto take for this issue are also necessary.

With regard to battery packs having a lower face reinforced with metal,the inner temperature of such battery packs rises when thetransportation machinery makes contact with flame from a road, possiblycausing thermal runaway of the cells and ignition. It is thereforenecessary to prevent fire from penetrating into the battery packs andprevent an increase in the temperature inside the battery packs. Fuelcell vehicles are equipped with a hydrogen tank which has a risk ofexplosion, and thus measures to deal with external flames are alsonecessary. Moreover, with miniaturization and the reduction of weight ofhydrogen tanks for space expansion of vehicle compartments or freelayout design, if the number of equipped hydrogen tanks is increased,the parts possibly to contact fire may not be identified. Thus, coversto enclose the entirety of a battery pack or a hydrogen tank also needmeasures against heat or ignition.

The present invention can provide a molded article having high heatresistance, high flame retardancy, excellent impact resistance,excellent chemical resistance, and excellent transparency. The moldedarticle can suitably be used as a member of transportation machinery orbattery systems.

Examples of the transportation machinery include automobiles such asgasoline-powered vehicles, hybrid vehicles, electric vehicles, and fuelcell vehicles; motorcycles such as gasoline-powered motorcycles, hybridmotorcycles, and electric motorcycles; bicycles such as power assistedbicycles; railway vehicles; vessels; and aircraft.

Examples of the member of transportation machinery include mechanismmembers, interior members, exterior members, glass, and light covers.

Examples of the mechanism members include cooling pipes, air bag covers,air ducts, and heater units.

Examples of the interior members include ceiling, instrument panels,console boxes, arm rests, seat belt buckles, switches, and door trims.

Examples of the exterior members include emblems, number plate housings,bumper cores, and under covers.

Examples of the battery systems include primary batteries such as nickelmanganese batteries, lithium batteries, and zinc-air batteries;secondary batteries such as nickel hydrogen batteries, lithium-ionbatteries, and lead storage batteries; solar cells such as silicon solarcells, dye-sensitized solar cells, and perovskite solar cells; and fuelcells such as solid polymer fuel cells, alkali fuel cells, phosphoricacid fuel cells, and solid oxide fuel cells.

Examples of the member of battery systems include battery cases, batterycooling water jackets, hydrogen tank covers, connectors, and insulationsheets.

Advantageous Effects of Invention

The present invention can provide a chlorinated polyvinyl chloride resinthat enables the production of a molded article that maintains highadhesion strength even when used in a form subjected to high pressureand is less susceptible to defects such as cracks due to insufficientstrength, as well as a resin composition for molding and a moldedarticle each including the chlorinated polyvinyl chloride resin. Thepresent invention also makes it possible to achieve high bondability ina short time.

DESCRIPTION OF EMBODIMENTS

The present invention is hereinafter described in more detail withreference to examples; however, the present invention should not belimited to these examples.

Example 1

A glass-lined reaction vessel having an inner capacity of 300 L wascharged with 130 kg of ion-exchanged water and 50 kg of a polyvinylchloride resin having an average degree of polymerization of 1,000. Theywere stirred to disperse the polyvinyl chloride resin in water toprepare an aqueous suspension, and then the inside of the reactionvessel was heated to raise the temperature of the aqueous suspension to70° C. Subsequently, the inside of the reaction vessel was depressurizedto remove oxygen (oxygen content 100 ppm). Thereafter, with stirring,chlorine (oxygen content 50 ppm) was introduced at a partial pressure ofchlorine of 0.04 MPa, and the suspension was irradiated with ultravioletlight having a wavelength of 365 nm at an irradiation intensity of 160 Wusing a high-pressure mercury lamp, thereby starting chlorinationreaction.

Then, the chlorination temperature was kept at 70° C., the partialpressure of chlorine was kept at 0.04 MPa, and the average chlorineconsumption rate was adjusted to 0.02 kg/PVC-kg-5 min. When the amountof added chlorine reached 9.5% by mass, the ultraviolet irradiationusing the high-pressure mercury lamp and the chlorine gas supply wereterminated, whereby chlorination was terminated.

Subsequently, unreacted chlorine was removed by nitrogen gas aeration,and the obtained chlorinated polyvinyl chloride resin slurry wasneutralized with sodium hydroxide, washed with water, and dehydrated ina centrifuge (produced by Tanabe Tekkosho K. K., 0-15 model) for threeminutes.

After dehydration, 0.1 parts by mass (0.05 kg) of 2-ethylhexylthioglycolate (produced by FUJIFILM Wako Pure Chemical Corporation) wasadded to 100 parts by mass (50 kg) of the chlorinated polyvinyl chlorideresin at 200 g/min. This was followed by stationary drying at 90° C.Thus, a powdery, photo-chlorinated polyvinyl chloride resin (amount ofadded chlorine: 9.5% by mass) was obtained.

Comparative Example 1

A glass-lined reaction vessel having an inner capacity of 300 L wascharged with 130 kg of ion-exchanged water and 50 kg of a polyvinylchloride resin having an average degree of polymerization of 1,000. Theywere stirred to disperse the polyvinyl chloride resin in water toprepare an aqueous suspension, and then the inside of the reactionvessel was heated to raise the temperature of the aqueous suspension to140° C. Subsequently, the inside of the reaction vessel wasdepressurized to remove oxygen (oxygen content 100 ppm). Thereafter,with stirring, chlorine (oxygen content 50 ppm) was introduced at apartial pressure of chlorine of 0.04 MPa, thereby starting thermalchlorination.

Then, the chlorination temperature was kept at 140° C. and the partialpressure of chlorine was kept at 0.4 MPa. After the amount of addedchlorine reached 4.4% by mass, addition of a 200 ppm hydrogen peroxidesolution was started at 15 ppm/Hr in terms of hydrogen peroxide relativeto the polyvinyl chloride resin, and the average chlorine consumptionrate was adjusted to 0.05 kg/PVC-kg-5 min. When the amount of addedchlorine reached 9.5% by mass, the supply of hydrogen peroxide solutionand chlorine gas was terminated, whereby chlorination was terminated.

Subsequently, unreacted chlorine was removed by nitrogen gas aeration,and the obtained chlorinated polyvinyl chloride resin slurry wasneutralized with sodium hydroxide, washed with water, and dehydrated ina centrifuge (produced by Tanabe Tekkosho K. K., 0-15 model) for threeminutes. This was followed by stationary drying at 90° C. Thus, apowdery, thermally chlorinated polyvinyl chloride resin (amount of addedchlorine: 9.5% by mass) was obtained.

Examples 2 to 8 and Comparative Examples 2 and 3

A powdery chlorinated polyvinyl chloride resin was obtained as inExample 1 except that the average degree of polymerization and thecharged amount of the polyvinyl chloride resin, the amount of the sulfurcompound added, the reaction temperature, the average chlorineconsumption rate, the drying temperature, and the drying time werechanged as shown in Table 1.

(Evaluation)

The chlorinated polyvinyl chloride resins obtained in the examples andthe comparative examples were evaluated as follows. Table 1 shows theresults.

(1) Pulse NMR Measurement

The obtained powdery chlorinated polyvinyl chloride resin was placed ina glass sample tube having a diameter of 10 mm (produced by BRUKER,Product No. 1824511, 10 mm in diameter, 180 mm in length, flat bottom)so as to fall within the measurement range of a pulse NMR apparatus. Thesample tube was set in the pulse NMR apparatus (produced by BRUKER, “theminispec mq20”) and subjected to measurement by the solid echo method at30° C. under the conditions below, thereby obtaining a free inductiondecay curve of 1H spin-spin relaxation.

<Solid Echo Method>

Scans: 128 timesRecycle delay: 1 secAcquisition scale: 0.5 ms

The free induction decay curve was subjected to waveform separation intotwo curves derived from the A₃₀ component and the B₃₀ component. Thewaveform separation was performed by fitting using a Gaussian model. Thepercentages of the two components were determined from the curvesderived from the components obtained in the measurement.

Using analysis software “TD-NMRA (Version 4.3, Rev. 0.8)” produced byBRUKER, a Gaussian-model fitting was applied to the A₃₀ component andB₃₀ component in conformity with the product manual.

The following equation was used in the fitting.

$\begin{matrix}{Y = {{A \times {\exp( {{- \frac{1}{2}} \times ( \frac{t}{T_{A}} )^{2}} )}} + {B \times {\exp( {{- \frac{1}{2}} \times ( \frac{t}{T_{B}} )^{2}} )}} + {C \times {\exp( {- \frac{1}{T_{C}}} )}}}} & \lbrack {{Math}.1} \rbrack\end{matrix}$

In the formula, A represents the percentage of the A₃₀ component, Brepresents the percentage of the B₃₀ component, T_(A) represents therelaxation time of the A₃₀ component, T_(B) represents the relaxationtime of the B₃₀ component, and t represents time.

The A₃₀ component and the B₃₀ component are components defined in orderof shorter relaxation time in pulse NMR measurement.

(Measurement after Heating at 200° C. for Five Minutes)

The obtained powdery chlorinated polyvinyl chloride resin in an amountof 300 g was placed in an aluminum tray, uniformly levelled, and thenheated in an oven (produced by Toyo Seiki Seisaku-Sho, Ltd., CO-02) at200° C. for five minutes. Thereafter, the percentages of the twocomponents (A₃₀ component and B₃₀ component), the relaxation time T5_(A)of the A₃₀ component, and the relaxation time T5_(B) of the B₃₀component were determined by the same method as above.

(Measurement after Heating at 200° C. for 20 Minutes)

The obtained powdery chlorinated polyvinyl chloride resin in an amountof 300 g was placed in an aluminum tray, uniformly levelled, and thenheated in an oven (produced by Toyo Seiki Seisaku-Sho, Ltd., CO-02) at200° C. for 20 minutes. Thereafter, the percentages of the twocomponents (A₃₀ component and B₃₀ component), the relaxation timeT20_(A) of the A₃₀ component, and the relaxation time T20_(B) of the B₃₀component were determined by the same method as above.

The T5_(B)/T_(B) and the T5_(B)/T20_(B) were calculated from theobtained T_(B), T5_(B), and T20_(B).

(2) Measurement of Amount of Added Chlorine

The amount of added chlorine was measured for each of the obtainedchlorinated polyvinyl chloride resins in conformity with JIS K 7229.

(3) Molecular Structure Analysis

The molecular structure of each of the obtained chlorinated polyvinylchloride resins was analyzed in conformity with the NMR measurementmethod described in R. A. Komoroski, R. G. Parker, J. P. Shocker,Macromolecules, 1985, 18, 1257-1265 so as to determine the amount of thestructural units (a) and (b) relative to the total number of moles ofthe structural units (a), (b), and (c).

The NMR measurement conditions were as follows.

Apparatus: FT-NMRJEOLJNM-AL-300

Measured nuclei: 13C (proton complete decoupling)

Pulse width: 90°

PD: 2.4 sec

Solvent: o-dichlorobenzene: deuterated benzene (C5D5)=3:1

Sample concentration: about 20%

Temperature: 110° C.

Reference material: central signal for benzene set to 128 ppm

Number of scans: 20,000

(4) Measurement of Sulfur Content of Chlorinated Polyvinyl ChlorideResin

An amount of 300 parts by mass of THF was added to 10 parts by mass ofeach of the obtained chlorinated polyvinyl chloride resins, stirred for24 hours for dissolution, followed by further stirring in a centrifuge(produced by Kokusan Co., Ltd., H-200NR) at 14,000 rpm for 1 hour toprecipitate insoluble components. The insoluble components were filteredout, and to the filtrate was added 1,000 parts by mass of methanol toreprecipitate the resin. While the resin was washed with methanol,suction filtration was performed using an aspirator (produced by AS ONECorporation, GAS-1N) to separate the resin from the filtrate. In thismanner, a sulfur-bound resin was obtained. The resin was put in a vacuumdrier (produced by Tokyo Rikakikai Co., Ltd., VOS-451SD) and dried at80° C. for 24 hours. Combustion IC was performed to detect CS bonds. Theobtained sample was weighed in a ceramic boat, and then burned in anautomatic sample combustion device. The generated gas was captured in 10mL of an absorber liquid. This absorber liquid was adjusted to 15 mLwith ultrapure water, and subjected to IC quantitative analysis. After alinear approximation of a SO₄ ²⁻ anion calibration curve by measurementof a reference substance, the sample was measured to quantify the sulfurcontent (mass ppm) of the chlorinated polyvinyl chloride resin.

The measurement conditions for the automatic combustion device are asfollows.

Device: AQF-2100H, produced by Mitsubishi Chemical Analytech

Inlet temperature: 1,000° C.

Outlet temperature: 1,100° C.

Gas flow rate O₂: 400 mL/min

Gas flow rate Ar: 200 mL/min

Ar water supply unit: 100 mL/min

The conditions for IC are as follows.

Device: ICS-5000, produced by Thermo Fisher Scientific

Separation column: Dionex IonPac AS18-4 μm (2 mm×150 mm)

Guard column: Dionex IonPac AG18-4 μm (2 mm×30 mm)

Suppressor system: Dionex AERS-500 (external mode)

Detector: conductivity detector

Eluent: aqueous KOH solution (eluent generator EGC500)

Eluent flow rate: 0.25 mL/min

Sample injection volume: 100 μL

(5) Adhesion Evaluation (Preparation of Pipe)

An amount of 4.0 parts by mass of an impact resistance modifier wasadded to 100 parts by mass of each of the obtained chlorinated polyvinylchloride resins. Then, 0.5 parts by mass of a thermal stabilizer wasadded and mixed. The impact resistance modifier used was Kane Ace B-564(produced by Kaneka Corporation, methyl methacrylate-butadiene-styrenecopolymer). The thermal stabilizer used was TVS#1380 (produced by NittoKasei Co., Ltd., organotin stabilizer).

Further, 1.5 parts by mass of a polyethylene lubricant (produced byMitsui Chemicals, Inc., Hiwax 220MP) and 0.2 parts by mass of a fattyacid ester lubricant (produced by Emery Oleochemicals Japan Ltd., LOXIOLG-32) were added. They were then uniformly mixed in a super mixer toprepare a chlorinated polyvinyl chloride resin composition.

The obtained chlorinated polyvinyl chloride resin composition wassupplied to a conical counter-rotating twin screw extruder (produced byOsada Seisakusho, SLM-50) having a diameter of 50 mm and formed intopipes at a resin temperature of 200° C., each pipe having an outerdiameter of 26.7 mm and a wall thickness of 2.4 mm.

(Preparation of Joint)

An amount of 5.0 parts by mass of an impact resistance modifier wasadded to 100 parts by mass of a chlorinated polyvinyl chloride resin(produced by Sekisui Chemical Co., Ltd., HA-24KL). Further, 3.0 parts bymass of a thermal stabilizer was added and mixed. The impact resistancemodifier used was Kane Ace M-511 (produced by Kaneka Corporation, methylmethacrylate-butadiene-styrene copolymer). The thermal stabilizer usedwas TVS#1380 (produced by Nitto Kasei Co., Ltd., organotin stabilizer).

Further, 2.0 parts by mass of a polyethylene lubricant (produced byMitsui Chemicals, Inc., Hiwax 220MP) and 0.3 parts by mass of a fattyacid ester lubricant (produced by Emery Oleochemicals Japan Ltd., LOXIOLG-32) were added. They were then uniformly mixed in a super mixer toprepare a chlorinated polyvinyl chloride resin composition.

The obtained chlorinated polyvinyl chloride resin composition wassupplied to a conical counter-rotating twin screw extruder (produced byOsada Seisakusho, OSC-30) having a diameter of 30 mm and formed intopellets at a resin temperature of 190° C. The obtained pellets weresupplied to an injection molding machine (produced by JSW, J350ADS) andformed into a socket having an outer diameter of 34.7 mm and an innerdiameter of 26.9 mm.

(Preparation of Assembled Sample)

Two of the obtained pipes were cut to a length of 20 cm and bonded tothe two ends of the obtained joint using an adhesive (produced by IPS,WELD-ON 724). The workpiece was then left to stand at 23° C. for 14days, and left to stand in an oven (produced by Toyo Seiki Seisaku-Sho,Ltd., CO-02) at 82° C. for 2 days, whereby an assembled sample wasobtained.

(Adhesion Evaluation)

The inside of the obtained assembled sample was filled with water. Thetest was started by pressurizing the pipes to a hoop stress of 15.93 MPausing a hydrostatic pressure resistance tester (produced by IPT,1662-0021) in an atmosphere adjusted to 65° C. with an oven. The timeuntil a disconnection occurred between the pipe and joint to which theadhesive was applied was measured.

The adhesion was evaluated as “o” (Good) when no disconnection wasobserved after 1,000 hours from the start of the test, and evaluated as“x” (Poor) when a disconnection occurred by 1,000 hours.

(6) Evaluation of Short-Term Bondability

(Preparation of pipe) and (Preparation of joint) were performed in thesame manner as in “(5) Adhesion evaluation”. (Preparation of assembledsample) and (Evaluation of short-term bondability) were then performedas follows.

(Preparation of Assembled Sample)

Two of the obtained pipes were cut to a length of 20 cm and bonded tothe two ends of the obtained joint using an adhesive (produced by IPS,WELD-ON 724). The workpiece was then left to stand at 23° C. for 24hours, and left to stand in an oven (produced by Toyo Seiki Seisaku-Sho,Ltd., CO—O2) at 82° C. for two days, whereby an assembled sample wasobtained.

(Evaluation of Short-Term Bondability)

The inside of the obtained assembled sample was filled with water. Thetest was started by pressurizing the pipes to an actual pressure of 3.6MPa using a hot internal pressure creep tester (produced by YONEKURAMFG. Co., Ltd.) in an atmosphere adjusted to 82° C. with an oven. Thetime until a disconnection occurred between the pipe and joint to whichthe adhesive was applied was measured, and the short-term bondabilitywas evaluated in accordance with the following criteria.

o (Good): No disconnection was observed after six minutes after thestart of the test.x (Poor): A disconnection occurred by six minutes after the start of thetest.

(7) Molded Article Strength Evaluation

The presence or absence of cracks or fractures in the pipes and jointwere determined after “(5) Adhesion evaluation”, and the molded articlestrength was evaluated in accordance with the following criteria.

o (Good): No crack or fracture was observed after 1,000 hours.x (Poor): Cracks or fractures were observed by 1,000 hours.

TABLE 1 Example Comparative Example 1 2 3 4 5 6 7 8 1 2 3 Production RawAverage degree of polymerization 1000 1000 1000 700 1000 1000 1000 10001000 1000 1000 method material Charged amount kg 50 50 50 50 50 50 50 5050 25 50 PVC Water Ion-exchanged water kg 130 130 130 130 130 130 130130 130 130 130 Chlorination Reaction temperature °C 70 60 80 70 70 7070 70 140 70 70 conditions Reaction pressure Mpa 0.04 0.04 0.04 0.040.04 0.04 0.04 0.04 0.40 0.04 0.04 PVC + water kg 180 180 180 180 180180 180 180 180 155 180 Resin concentration mass % 28 28 28 28 28 28 2828 28 16 28 (PVC/(PVC + water))*100 Average chlorine consumption ratekg/pvc-kg · 0.02 0.015 0.02 0.02 0.02 0.02 0.02 0.02 0.05 0.04 0.02 5min UV wavelength nm 365 365 365 365 365 365 365 365 — 365 365 200 ppmhydrogen peroxide ppm/hr — — — — — — — — 15 0 — Amount of 2-ethylhexylthio- parts by 0.1 0.1 0.1 0.1 0.1 0.05 5.0 0.1 0 0 0.1 glycolate addedmass Drying temperature °C 90 90 90 90 90 90 90 120 90 90 50 Drying timehr 12 12 12 12 12 12 12 6 12 12 72 Chlorinated Amount of added chlorinemass % 9.5 9.5 9.5 9.5 7.3 9.5 9.5 9.5 9.5 9.5 9.5 polyvinyl Sulfurcontent of resin mass ppm 13 13 12 12 12 11 18 13 0 0 3 chlorideStructure Structural unit (a) —CH₂—CHCl— mol % 43.4 42.1 40.1 40.9 48.543.4 43.4 43.4 42.0 31.3 43.4 resin Structural unit (b) —CH₂—CCl₂— mol %24.2 22.7 36.4 19.1 22.1 24.2 24.2 24.2 20.2 39.3 24.2 Pulse NMR NotRelaxation T_(A) ms 0.0114 0.0114 0.0114 0.0114 0.0114 0.0112 0.01140.0114 0.0114 0.0114 0.0114 [30° C. heated time T_(B) ms 0.1531 0.15380.1544 0.1485 0.1809 0.1975 0.1187 0.1510 0.1578 0.1565 0.1780 measure-Percentage A₃₀ % 97.9 97.9 97.8 98.5 98.4 98.8 97.4 97.8 98.7 98.1 97.7ment] B₃₀ % 2.1 2.1 2.2 1.5 1.6 1.2 2.6 2.2 1.3 1.9 2.3 After RelaxationT5_(A) ms 0.0114 0.0114 0.0114 0.0114 0.0114 0.0112 0.0114 0.0114 0.01150.0113 0.0114 heating at time T5_(B) ms 0.1265 0.1398 0.1221 0.13160.1518 0.1774 0.0964 0.1206 0.1599 0.1092 0.1718 200° C. Percentage A₃₀% 97.7 97.7 97.7 98.5 98.4 98.8 97.4 97.8 98.9 97.8 980 for 5 B₃₀ % 2.32.3 2.3 1.5 1.6 1.2 2.6 2.2 1.1 2.2 2.0 minutes After Relaxation T20_(A)ms 0.0114 0.0114 0.0114 0.0114 0.0114 0.0112 0.0114 0.0114 0.0116 0.01140.1114 heating at time T20_(B) ms 0.1377 0.1461 0.1423 0.1583 0.16280.1893 0.1104 0.1307 0.1599 0.1549 0.1802 200° C. Percentage A₃₀ % 97.997.9 97.9 98.6 98.2 98.9 97.3 97.9 99.1 980 98.1 for 20 B₃₀ % 2.1 2.12.1 1.4 1.8 1.1 2.7 2.1 0.9 2.0 1.9 minutes Relaxation time ratioT5_(B)/T_(B) % 82.6 90.9 79.1 88.6 83.9 89.8 81.2 79.9 101.3 69.8 96.5Relaxation time ratio T5_(B)/T20_(B) % 91.9 95.7 85.8 83.1 93.2 93.787.3 92.3 100.0 70.5 95.3 Evaluation Adhesion Occurrence of hr 1000 10001000 1000 1000 1000 1000 1000 40 1000 800 disconnection Rating ○ ○ ○ ○ ○○ ○ ○ x ○ x Short-term bondability Disconnection min 6 6 6 6 6 6 6 6 4 56 time Rating ○ ○ ○ ○ ○ ○ ○ ○ x x ○ Molded article strength Rating ○ ○ ○○ ○ ○ ○ ○ ○ x ○

INDUSTRIAL APPLICABILITY

The present invention can provide a chlorinated polyvinyl chloride resinthat enables the production of a molded article that maintains highadhesion strength even when used in a form subjected to high pressureand is less susceptible to defects such as cracks due to insufficientstrength, as well as a resin composition for molding and a moldedarticle each including the chlorinated polyvinyl chloride resin.

1. A chlorinated polyvinyl chloride resin comprising two componentsincluding a A₃₀ component and a B₃₀ component, the A₃₀ component and theB₃₀ component being determined by measuring the resin by a solid echomethod using pulse NMR at 30° C. to give a free induction decay curve of¹H spin-spin relaxation, and subjecting the free induction decay curveto waveform separation into two curves derived from the A₃₀ componentand the B₃₀ component in order of shorter relaxation time using theleast square method, and having a ratio of T5_(B) to T_(B)[T5_(B)/T_(B)] of 76% or more and less than 96%, where T_(B) is arelaxation time of the B₃₀ component and T5_(B) is a relaxation time ofthe B₃₀ component after heating at 200° C. for five minutes.
 2. Thechlorinated polyvinyl chloride resin according to claim 1, having aratio of T5_(B) to T20_(B) [T5_(B)/T20_(B)] of 76% or more and less than96%, where T5_(B) is the relaxation time of the B₃₀ component afterheating at 200° C. for 5 minutes and T20_(B) is a relaxation time of theB₃₀ component after heating at 200° C. for 20 minutes.
 3. A resincomposition for molding, comprising the chlorinated polyvinyl chlorideresin according to claim
 1. 4. A molded article molded from the resincomposition for molding according to claim 3.